High carbon concentration biomass and biosolids slurry preparation using a hydro-thermal pretreatment

ABSTRACT

Provided is a process where the biomass and bisolids are hydrothermally treated under a reductive gas. Using this process a high carbon content pumpable mixture of biomass and biosolid slurry is produced with a viscosity value of less than 1.5.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional No. 61/309,296filed on Mar. 1, 2010.

This application is also a continuation-in-part of, and claims thebenefit of U.S. patent application Ser. No. 12/286,165, filed on Sep.29, 2008, which is also a continuation-in-part of U.S. patentapplication Ser. No. 11/879,456, filed Jul. 16, 2007, which is acontinuation-in-part of U.S. patent application Ser. No. 11/489,299 (nowabandoned). This application is also a continuation-in-part of, andclaims the benefit of, patent application Ser. No. 12/400,640, filedMar. 9, 2009, which is a continuation-in-part of, and claims the benefitof patent application Ser. No. 11/879,241, filed Jul. 16, 2007, which isa continuation-in-part of patent application Ser. No. 11/489,298, filedJul. 18, 2006. Patent application Ser. No. 12/400,640 is also acontinuation-in-part of, and claims the benefit of, patent applicationSer. No. 10/911,348, filed Aug. 3, 2004, which is a continuation-in-partof International Application PCT/US03/03489, with an internationalfiling date of Feb. 4, 2003, which claims the benefit of U.S.Provisional Application Ser. No. 60/355,405, filed Feb. 5, 2002. Thisapplication is also a continuation-in-part of, and claims the benefitof, patent application Ser. No. 11/879,266, filed Jul. 16, 2007, whichis a continuation-in-part of, and claims the benefit of, applicationSer. No. 11/489,308, filed Jul. 18, 2006.

All of the above cited applications are incorporated herein by referencein their entirety.

FIELD OF THE INVENTION

The field of the invention relates to a hydrothermal treatment processfor preparing a high carbon concentration slurry formed with biosolidswaste and biomass mixture that could be pumped in a pressurizedcondition.

BACKGROUND OF THE INVENTION

Biosolids (aka treated municipal sewage sludge), the residue producedfrom waste water treatment process, are produced at a rate of about 5.6million dry tons per year (ton=2000 lb) in the United States (US) [1].In general, dry weight per capita production of biosolid resulting fromprimary, secondary and even tertiary treatment is in average 90 g perperson per day [2]. About 61% of the total biosolids currently producedin USA is disposed of through land farming, 17% disposed of in licensedmunicipal solid waste landfills, 20% incinerated, and about 1% disposedof in surface disposal units. This is by far the largest in volume amongthe constituents removed by the effluent treatment process; therefore,it's handling methods and disposal techniques are a matter of greatconcern.

The biosolids produced from the wastewater treatment process is usuallyin liquid or slurry form. The concentration of solids ranges between0.25-25% solids by weight. The solid fraction varies between the abovelimits due to the different methods of the effluent treatment. In themunicipal wastewater treatment plant, before disposal, the biosolids hasto be treated to eliminate the bacteria, viruses and organic pollutants.

Recently, the sea disposal of sewage sludge has been prohibited, inorder to protect the marine environment. The agricultural reuse as afertilizer, incineration and land-filling has become the principalbiosolid disposal method. The latest trends in the field of biosolidutilization are combustion, wet oxidation, pyrolysis, gasification andco-combustion of sewage sludge with other materials for further use asenergy source as well as applications in some other areas such asforestry, land reclamation, etc. These applications have generatedsignificant scientific interest. A previous invention of SteamHydro-gasification technology [3] has been demonstrated to efficientlyconvert carbonaceous materials into syngas (a mixture of majorly CO andH₂). The application of such technology requires external water sourceand a careful control over the water to carbon ratio inside thefeedstocks. Biosolids discharged from waste water treatment plantscontains 70% to 97.5% of water based on from which process the biosolidsis collected. Traditional disposal of the biosolids waste is costly andenvironmentally unfriendly. Therefore, a co-utilization of biosolidswaste with wasted biomass can be carried out by co-gasification of bothfeedstocks. The transportation and feed of such feedstocks inpressurized gasification reactor is conventionally done by using dryfeed (lock hoppers). While recently, it was widely acknowledged thatslurry feed has several advantages over dry feed causing by its natureof operation (Table 1). So a hydro-thermal pretreatment process isinvented here to convert the high carbon concentration biomass andbiosolids mixture into a slurry formed feedstocks.

TABLE 1 Comparison of Feeding Methods in Pressurized Condition⁴ Dry Feed(locker hopper) Slurry feed Method Gas blow Pump pressurization SystemComplex Simple Operation Expensive Economical Duration UnreliableReliable

The biosolids produced from the wastewater treatment process is usuallyin liquid or slurry form. The concentration of solids ranges between0.25-25% solids by weight. The solid fraction varies between the abovelimits due to the different methods of the effluent treatment. In themunicipal wastewater treatment plant, before disposal, the biosolids hasto be treated to eliminate the bacteria, viruses and organic pollutants.

There is a need to identify new sources of chemical energy and methodsfor its conversion into alternative transportation fuels, driven by manyconcerns including environmental, health, safety issues, and theinevitable future scarcity of petroleum-based fuel supplies. The numberof internal combustion engine fueled vehicles worldwide continues togrow, particularly in the midrange of developing countries. Theworldwide vehicle population outside the U.S., which mainly uses dieselfuel, is growing faster than inside the U.S. This situation may changeas more fuel-efficient vehicles, using hybrid and/or diesel enginetechnologies, are introduced to reduce both fuel consumption and overallemissions. Since the resources for the production of petroleum-basedfuels are being depleted, dependency on petroleum will become a majorproblem unless non-petroleum alternative fuels, in particularclean-burning synthetic diesel fuels, are developed. Moreover, normalcombustion of petroleum-based fuels in conventional engines can causeserious environmental pollution unless strict methods of exhaustemission control are used. A clean burning synthetic diesel fuel canhelp reduce the emissions from diesel engines.

The production of clean-burning transportation fuels requires either thereformulation of existing petroleum-based fuels or the discovery of newmethods for power production or fuel synthesis from unused materials.There are many sources available, derived from either renewable organicor waste carbonaceous materials. Utilizing carbonaceous waste to producesynthetic fuels is an economically viable method since the input feedstock is already considered of little value, discarded as waste, anddisposal is often polluting.

Liquid transportation fuels have inherent advantages over gaseous fuels,having higher energy densities than gaseous fuels at the same pressureand temperature. Liquid fuels can be stored at atmospheric or lowpressures whereas to achieve liquid fuel energy densities, a gaseousfuel would have to be stored in a tank on a vehicle at high pressuresthat can be a safety concern in the case of leaks or sudden rupture. Thedistribution of liquid fuels is much easier than gaseous fuels, usingsimple pumps and pipelines. The liquid fueling infrastructure of theexisting transportation sector ensures easy integration into theexisting market of any production of clean-burning synthetic liquidtransportation fuels.

The availability of clean-burning liquid transportation fuels is anational priority. Producing synthesis gas (which is a mixture ofhydrogen and carbon monoxide) cleanly and efficiently from carbonaceoussources, that can be subjected to a Fischer-Tropsch type process toproduce clean and valuable synthetic gasoline and diesel fuels, willbenefit both the transportation sector and the health of society. AFischer-Tropsch type process or reactor, which is defined herein toinclude respectively a Fischer-Tropsch process or reactor, is anyprocess or reactor that uses synthesis gas to produce a liquid fuel.Similarly, a Fischer-Tropsch type liquid fuel is a fuel produced by sucha process or reactor. A Fischer-Tropsch type process allows for theapplication of current state-of-art engine exhaust after-treatmentmethods for NO_(x) reduction, removal of toxic particulates present indiesel engine exhaust, and the reduction of normal combustion productpollutants, currently accomplished by catalysts that are poisonedquickly by any sulfur present, as is the case in ordinary stocks ofpetroleum derived diesel fuel, reducing the catalyst efficiency.Typically, Fischer-Tropsch type liquid fuels, produced from biomassderived synthesis gas, are sulfur-free, aromatic free, and in the caseof synthetic diesel fuel have an ultrahigh cetane value.

Biomass material is the most commonly processed carbonaceous waste feedstock used to produce renewable fuels. Biomass feed stocks can beconverted to produce electricity, heat, valuable chemicals or fuels.California tops the nation in the use and development of several biomassutilization technologies. For example, in just the Riverside County,California area, it is estimated that about 4000 tons of waste wood aredisposed of per day. According to other estimates, over 100,000 tons ofbiomass per day are dumped into landfills in the Riverside Countycollection area. This waste comprises about 30% waste paper orcardboard, 40% organic (green and food) waste, and 30% combinations ofwood, paper, plastic and metal waste. The carbonaceous components ofthis waste material have chemical energy that could be used to reducethe need for other energy sources if it can be converted into aclean-burning fuel. These waste sources of carbonaceous material are notthe only sources available. While many existing carbonaceous wastematerials, such as paper, can be sorted, reused and recycled, for othermaterials, the waste producer would not need to pay a tipping fee, ifthe waste were to be delivered directly to a conversion facility. Atipping fee, presently at $30-$35 per ton, is usually charged by thewaste management agency to offset disposal costs. Consequently not onlycan disposal costs be reduced by transporting the waste to awaste-to-synthetic fuels processing plant, but additional waste would bemade available because of the lowered cost of disposal.

The burning of wood in a wood stove is a simple example of using biomassto produce heat energy. Unfortunately, open burning of biomass waste toobtain energy and heat is not a clean and efficient method to utilizethe calorific value. Today, many new ways of utilizing carbonaceouswaste are being discovered. For example, one way is to produce syntheticliquid transportation fuels, and another way is to produce energetic gasfor conversion into electricity.

Using fuels from renewable biomass sources can actually decrease the netaccumulation of greenhouse gases, such as carbon dioxide, whileproviding clean, efficient energy for transportation. One of theprincipal benefits of co-production of synthetic liquid fuels frombiomass sources is that it can provide a storable transportation fuelwhile reducing the effects of greenhouse gases contributing to globalwarming. In the future, these co-production processes could provideclean-burning fuels for a renewable fuel economy that could be sustainedcontinuously.

A number of processes exist to convert coal and other carbonaceousmaterials to clean-burning transportation fuels, but they tend to be tooexpensive to compete on the market with petroleum-based fuels, or theyproduce volatile fuels, such as methanol and ethanol that have vaporpressure values too high for use in high pollution areas, such as theSouthern California air-basin, without legislative exemption from cleanair regulations. An example of the latter process is the Hynol MethanolProcess, which uses hydro-gasification and steam reformer reactors tosynthesize methanol using a co-feed of solid carbonaceous materials andnatural gas, and which has a demonstrated carbon conversion efficiencyof >85% in bench-scale demonstrations.

Of particular interest to the present invention are processes developedmore recently in which a slurry of carbonaceous material is fed into ahydro-gasifier reactor. One such process was developed in ourlaboratories to produce synthesis gas in which a slurry of particles ofcarbonaceous material in water, and hydrogen from an internal source,are fed into a hydro-gasification reactor under conditions to generaterich producer gas. This is fed along with steam into a steam pyrolyticreformer under conditions to generate synthesis gas. This process isdescribed in detail in Norbeck et al. U.S. patent application Ser. No.10/503,435 (published as US 2005/0256212), entitled: “Production OfSynthetic Transportation Fuels From Carbonaceous Material UsingSelf-Sustained Hydro-Gasification.”

In a further version of the process, using a steam hydro-gasificationreactor (SHR) the carbonaceous material is heated simultaneously in thepresence of both hydrogen and steam to undergo steam pyrolysis andhydro-gasification in a single step. This process is described in detailin Norbeck et al. U.S. patent application Ser. No. 10/911,348 (publishedas US 2005/0032920), entitled: “Steam Pyrolysis As A Process to EnhanceThe Hydro-Gasification of Carbonaceous Material.” The disclosures ofU.S. patent application Ser. Nos. 10/503,435 and 10/911,348 areincorporated herein by reference.

All of these processes require the formation of a slurry of biomass thatcan be fed to the hydro-gasification reactor. To enhance the efficiencyof the chemical conversions taking place in these processes, it isdesirable to have a low water to carbon ratio, therefore a high energydensity, slurry, which also makes the slurry more pumpable. High solidscontent coal/water slurries have successfully been used in coalgasifiers in the feeding systems of pressurized reactors. A significantdifference between coal/water slurries and biomass/water slurries isthat coal slurries contain up to 70% solids by weight compared to about20% solids by weight in biomass slurries. Comparing carbon content, coalslurries contain up to about 50% carbon by weight compared to about8-10% carbon by weight in biomass slurries. The polymeric structure ifcell walls of the biomass mainly consists of cellulose, hemicelluloseand lignin. All of these components contain hydroxyl groups. Thesehydroxyl groups play a key role in the interaction between water andbiomass, in which the water molecules are absorbed to form a hydrogenbond. This high hyrgroscopicity of biomass is generally why biomassslurries are not readily produced with a high carbon content.

A number of processes have been developed to produce high carbon contentslurries for use as the feedstock for a hydro-gasifier. JGC Corporationin Japan developed the Biomass Slurry Fuel process, which, however mustbe carried out at semi-critical conditions, with a temperature of 310°C. and at a pressure of 2200 psi. The process converts high watercontent biomass into an aqueous slurry having a solids content of about70%, which is the same level as a coal/water slurry. However, it has tobe carried out under high energy conditions.

Texaco researchers developed a hydrothermal pretreatment process formunicipal sewage sludge that involves heating the slurry to 350° C.followed by a two stage flash evaporation, again requiring high energyconditions.

Traditionally, thermal treatment of wood is a well known technology inthe lumber industry to enhance the structural property of wood, but notto prepare a slurry. It decreases hygroscopicity and increases thedurability of lumber for construction. Polymeric chains are cleaved inthermal treatment, and accessible hydroxyl groups are reduced leading toa limited interaction with water compared to untreated wood

Aqueous liquifications of biomass samples have been carried out in anautoclave in the reaction temperature range of about 277-377° C. atabout 725-2900 psi, to obtain heavy oils rather than slurries,exemplified by the liquification of spruce wood powder at about 377° C.to obtain a 49% liquid yield of heavy oil. See A. Demirba§,“Thermochemical Conversion of Biomass to Liquid Products in the AqueousMedium”, Energy Sources, 27:1235-1243, 2005.

Our previous work (U.S. patent application Ser. No. 11/489,299)disclosed novel methods that enabled the production of a stable biomassslurry containing up to 60% solids by weight, so as to provide 20-40%carbon by weight in the slurry. However, it was not appreciated at thattime the optimal conditions required for using such biomass slurries inhydrogasification processes, such as the optimum viscosity of the slurryto be delivered/pumped.

BRIEF SUMMARY OF THE INVENTION

Provided is a process for producing a high carbon content biomass andbiosolid slurry using an optimum carbon to water mass ratio comprisingproviding an amount of biomass and an amount of biosolid to form aslurry mixture; and treating the mixture under a non-oxidative gas. Inone embodiment, the biomass used in the process has not been treatedwith an external source of water. In another embodiment, the biomass andbiosolid mixture is heated to a temperature in the range of 180 to 270°C., more particularly in the range of 210 to 240° C. and at a pressureof saturated water vapor pressure. In yet another embodiment, theoptimum carbon to water mass ratio for the process is between 1:2 to1:4; and more particularly at 1:3. In another embodiment, the highcarbon content biomass and biosolid slurry produced is utilized ineither a hydrogasifier or steam hydrogasifier.

In another embodiment, a process is provided that can produce a highcarbon content biomass and biosolid slurry with a viscosity value ofless than 1.5 under a shear rate of 102 s⁻¹; in a more particularembodiment, a viscosity of less than 1.0 pa·s under a shear rate of 102s⁻¹ can be obtained.

Provided is a steam hydrogasification process efficient for gasificationof both coal and biomass feedstocks, either alone or commingled. Theprocess can utilize water to provide an internal source of hydrogen andto control the synthesis gas ratio over a wide range [3]. This requiresthe formation of a slurry with a high carbon to water ratio, but with aviscosity to allow ease of handling during preparation, storage andtransfer to the reactor.

The present invention provides an energy efficient process forconverting biomass into a higher carbon content, high energy densityslurry. In particular, a coal water slurry is combined with a mixture ofwater and biomass, where the mixture is heated at a temperature andunder a pressure that are much lower used in than prior processes, butunder nitrogen, which enables a stable slurry to be obtained containingup to 60% solids by weight, so as to provide 20-40% carbon by weight inthe slurry. While ranges will be given in the detailed description, thetemperature is nominally about 200° C. under non-oxidative gas pressureof about 150 psi, conditions that are substantially less stringent thanthose required by the prior art.

In another embodiment, the coal slurry is provided in an amount wherebyto obtain a viscosity of less than 0.7 Pas for the high energy densityslurry.

In yet another embodiment the water to carbon ratio of the high energydensity slurry is approximately 2:1. In a further embodiment, thewater:carbon ratio of the high energy density slurry can be adjusted to3:1.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, reference isnow made to the following description taken in conjunction with theaccompanying drawings, in which:

FIG. 1 shows a flow diagram for one embodiment of the inventionregarding the mixing sequence of biomass and biosolids hydrothermaltreatment

FIG. 2 shows a graph representing the viscosity value of pretreatedbiosolids and biomass under shear rate of 102 s⁻¹ vs. water to carbonmass ratio in resultant slurries: change of initial biosolids to biomassmass ratio and initial biomass particle size (pretreatment temperatureof 240° C.).

DETAILED DESCRIPTION OF THE INVENTION

A new process for a pumpable “slurry formed” biomass and bisolidsmixture production has been devised. The goal of high carbon content inthe pumpable biomass and biosolids slurry was achieved by hydrothermaltreatment of biomass and bisolids mixtures at different mixing ratios.The mixtures were then hydrothermal treated under mild thermal condition(230° C.) and a pressure of 1500 psi. A reductive gas phase in headspace of the vessel was maintained by pressurization of hydrogen, orother reductive or inert gas, before the hydrothermal treatment process.The vessel was impeller agitated inside for well mixing of mixtureduring hydrothermal treatment.

Three mixing sequences were tested as shown in FIG. 1. It was found thatthe third mixing sequence, which is to mix biomass with biosolids beforehydrothermal treatment, gave the best result, it offered the highestcarbon content in the pumpable biomass and biosolids slurry. It offeredthe simplest way of one mixing step for the hydrothermal treatment. Italso offered direct utilization of water from biosolids with outexternal source of water to make slurry.

In another embodiment, water rather than biosolids can be used.

In another embodiment, the biosolids used to be mixed with the biomass

Biomass was grinded and was then mixed with biosolids with differentbiomass to biosolids ratio. The control over carbon content in thebiomass and biosolids slurries was carried out by mixing biomass withbiosolids with different mass ratio. The resultant slurries were testedby its rheology properties, such as viscosity values for different shearrate values. It was found with initial biomass particle sizes of lessthan 180 um, a slurry with carbon to water ratio of over 1:2.5, equally22.3 wt % of carbon in the slurry, was produced with a viscosity valueof less than 1.0 pa·s under a shear rate of 102 s⁻¹ (FIG. 2).

Gas analysis was also carried out for the resultant exhaust gas to seehow much carbon was lost through the gas phase after the hydrothermaltreatment process. It was found a negligible amount of carbon present inthe exhaust gas phase, no more than 1%. Most of the carbon was presentin the gas phase in forms of CO₂ and CO, small amount of hydrocarbonwith carbon numbers from 1 through 5 was also detected in the exhaustgas.

The above described high carbon content biomass and biosolid slurryproduced by one embodiment can be used generally in hydrogasifiers orsteam hydrogasifiers more particularly disclosed in U.S. Pat. No.7,500,997 and U.S. application Ser. No. 11/879,266 (filed on Jul. 16,2007), which are both hereby incorporated by reference in theirentirety.

The term ‘biomass” as used herein refers broadly to material which is,or is obtained from, agricultural products, wood and other plantmaterial, and/or vegetation; paper and cardboard, or any combinationthereof. The biomass at the desired weight percentage, generally from 30to 70 wt %, is mixed with water, or diluted sewage sludge/biosolids,while at a temperature in the range of 170 to 250° C., most preferablyabout 200° C., under non-oxidative gas pressure of 100 to 400 psi, mostpreferably about 150 psi. The mixture can be placed in an autoclave atroom temperature and ramped to the reaction temperature, or the vesselcan be preheated to the desired temperature before being pressurized.The reaction temperature can range from 10 minutes to an hour or more.

In one embodiment, the biomass that is later to be mixed with water, orbiosolids, does not undergo any prior drying or evaporation procedure toremove the water present in the biomass or to concentrate the biomass.

In another embodiment, the definition of biomass excludes sewage sludgeor biosolids. However, ‘diluted sewage sludge/biosolids’ can serve as asource of water to be mixed and heated with the biomass under pressurein the presence of the non-oxidative gas. The term ‘diluted sewagesludge/biosolids’ means sewage sludge/biosolids material that have notbeen heated/dried to evaporate their water content. Such diluted sewagesludge/biosolids can contain from 70% to 97.5%, or 75% to 97.5%;80-97.5%; 90-97.57% of water.

In another embodiment, biomass can include material from landfills.

In another embodiment, the biomass is not mixed with any water and thenlater condensed, or water evaporated, prior to being mixed withwater/biosolids and heated in the disclosed process under thenon-oxidative gas under pressure of 100 to 400 psi, most preferablyabout 150 psi.

In another embodiment, the biomass material used excludes material thathave been treated to anerobic and aerobic conditions.

In another embodiment, the high carbon content biomass and biosolidslurry does not require being mixed with coal prior to utilizing suchhigh carbon content biomass and biosolid slurry in a hydrogasifier orsteam hydrogasifier.

In one embodiment, the water content of the mixture of biomass andwater/biosolids, remains about the same after heating with thenon-oxidative gas under pressure of 100 to 400 psi, most preferablyabout 150 psi. In another embodiment, the final water content of themixture after heating with the non-oxidative gas under pressure of 100to 400 psi, is within 40%; or 30%, or 20%, or 10% or 5% or 1% of theoriginal mixture water content.

While any non-oxidative gas can be used, such as argon, helium,nitrogen, hydrogen, carbon dioxide, or gaseous hydrocarbons, or mixturesthereof, nitrogen is preferred because of its economic availability.Another preferred non-oxidative gas is hydrogen if available internallyfrom the process, and which can be particularly advantageous if carriedwith the slurry into a hydro-gasification reactor. While it is desirableto eliminate oxidative gas, one can use a commercial grade, or lesspure, of the non-oxidative gas so long as no substantial oxidation takesplace.

The following examples will illustrate the invention.

EXAMPLE 1

Referring to FIG. 1, a non-pumpable mixture of 50% biomass, consistingof pine tree particles in water is shown before treatment. Dry pinesawdust was obtained from American Wood Fibers and the dry White Cedarfrom Utah. The sawdust was ground using a commercially available coffeegrinder and sieved to <100 mesh (150 μm). For the wood pre-treatment, anautoclave system was set up. It consisted of an Autoclave EngineersEZE-Seal pressure vessel rated at 3,300 psi at 850° F. The wood sampleand deionized water were weighed and then well mixed by hand to evenwater distribution in a large beaker before putting it in the vessel.The amount of wood added was adjusted for moisture content. The vesselwas then weighed with contents, vacuumed and purged three times withargon, and finally pressurized to 100±1 psi. The temperature was rampedto operating temperature (210-230° C.) in about 30 minutes and then heldfor 30 minutes. Pressure and internal temperature were recorded using adata acquisition software. After holding for 30 minutes, application ofthe heat was stopped and the vessel was pulled out of the heater. Thevessel was left to cool to room temperature to allow collection of headspace gas and sample. Temperature and pressure were recorded beforecollection and then the vessel was weighed.

The result is shown in FIG. 2, which is a photograph of the slurry ofFIG. 1 after treatment, which was a pumpable slurry containing 50 wt. %solids in water. Analysis of the head space gas showed negligiblecarbon, indicating negligible carbon loss from the slurry.

EXAMPLE 2

The procedure of Example 1 was followed but the vessel was preheatedto >200° C. before being put in the heater. The autoclave was found toreach 230° C. in 15 minutes or less and then it was held for 30 minutes.The time needed to reach the target temperature did not have anoticeable physical impact on the resulting product

EXAMPLE 3

The method of Example 1 can be carried out but in which the startingmixture is non-pumpable agricultural waste containing 60 weight percentsolids. The result will be a pumpable slurry containing 60 wt. % solidsin water.

EXAMPLE 4

The method of Example 1 can be carried out but in which the startingmixture is vegetation containing nonpumpable 40 weight percent solids.The result will be a pumpable slurry containing 40 wt. % solids inwater.

The slurry of carbonaceous material resulting from the process of thisinvention can be fed into a hydro-gasifier reactor under conditions togenerate rich producer gas. This can be fed along with steam into asteam pyrolytic reformer under conditions to generate synthesis gas, asdescribed in Norbeck et al. U.S. patent application Ser. No. 10/503,435,referred to above. Alternatively, the resultant slurry can be heatedsimultaneously in the presence of both hydrogen and steam to undergosteam pyrolysis and hydro-gasification in a single step, as described indetail in Norbeck et al. U.S. patent application Ser. No. 10/911,348,referred to above.

Examples Related to Commingling Biomass and Coal Slurries

Others have concluded that the rheological properties of coal-waterslurries, such as shear stress and viscosity, are dependent on the typeof coal, solid loading, coal particle size and size distribution,temperature, and additives [5-7]. Other studies have addressed biomasssuspension and the effect of particle size on rheological properties ofcellulosic biomass slurries [8]. However, biomass slurry rheologicalstudies and its potential as a gasification feedstock when co-mingledwith coal have not been reported.

Provided now are novel results obtained by examining the rheologicalproperties and pumpability of various coal-water, wood-water, andcommingled wood-coal-water slurries. The major factors considered areparticle size, solid loading, viscosity, and a proprietary woodpretreatment procedure for the wood for the purpose of increasing thesolid water ratio. Finally, the maximum solid content of co-mingledcoal-wood slurries that are pumpable was evaluated.

At the time the above data was produced (for the above Examples 1-4) (asdisclosed in U.S. patent application Ser. No. 11/489,299) it was notappreciated that the pumpability of our hydrogasification process wouldbe obtained with a viscosity of less than 0.7 Pas. Given this previouslyundisclosed fact, and that the optimum water:carbon ratio of our processis 3:1, we set out to determine how the viscosities of our pretreatedbiomass slurries could be improved. The following experiments show thatone method of improving pumpability of biomass slurries is to comminglebiomass slurries with coal slurries.

EXAMPLE 5

Preparation of Coal and Wood Particles

Coal and wood particles were prepared from bituminous coal from Utah andpoplar sawdust. Each material was initially ground and then pulverizedin a pulverizing grinder. The pulverized particles were then sieved intothree particle size ranges: 0-150 μm, 150 μm-250 μm and 250 μm-500 μm.The particles were then dried in a vacuum oven for vaporization of themoisture content at 70° C. The analysis of the solid content of the coaland wood particles after the vaporization process was determined byThermometric Gravitation Analysis (TGA). The results of the TGA arepresented in Table 1. Finally, particles were mixed with water to formnumerous coal and wood slurries. The solid loading for coal-waterslurries ranged from 40 wt. % to 65 wt. % by every 5% and 5 wt. % to12.5 wt. % by every 2.5% for the wood-water slurries. Mixtures weresettled overnight for complete mixing of the particles and water andwere then gently stirred just before the rheological tests to avoidsettlement of particles. Harsh stirring was avoided to prevent small airbubbles which would impact the rheological tests.

TABLE 1 Coal particles Wood particles Ash content (wt. %) 7.6 0.6Moisture content (wt. %) 4.0 5.75 Volatile matter (wt. %) 36.2 72.8B. Pretreatment of Wood Slurry

In an actual working example, a portion of the prepared wood particleswithin the particle size of 150 μm-250 μm were pretreated using aproprietary method developed by our laboratory. The wood particles weremixed with water at solid weight percentages of 20 wt. %, 30 wt. %, and40 wt. %. The mixtures were then heated at 230° C. at 100 psi ofhydrogen for 30 min. The process was carried out in a sealed batchreactor; thus the difference in the solid content before and after thepretreatment was assumed to be negligible and was confirmed by thermalanalysis of the biomass slurry after pretreatment. The 20 wt. %pretreated biomass slurry was then mixed with up to 35 wt. % of the0-150 μm coal particles to form commingled biomass-coal-water slurries.

Although 20 wt % pretreated biomass slurry was mixed with up to 35 wt %of the 0-150 um coal particles, it is also possible to use 30 wt % or 40wt % wood particle preparations. Further mixtures can be heated at arange of between 180-300° C. at between 100-1000 psi of hydrogen forbetween 10-45 minutes. Also, although 35 w % of the 0-150 um coalparticles were used, it is possible to use instead 150 μm-250 μm and 250μm-500 μm size particles.

C. Determination of the Slurry Rheological Properties

Rheological properties of slurries were determined by using an AntonPaar Reolab QC rotational rheometer with temperature control. Therotational rheometer is a coaxial-cylinder rheometer with the centerrotor rotating at a defined speed or torque. A six-blade vane spinnerwith 1 inch outside diameter was utilized as the rotor. The reason foremploying a vane spinner as the rotor is that the vane-cup system causesmuch less error when testing large particles and has less impact on theslurry structure [9].

Pump selection for handling slurries for industry applications is basedon rheological data that are obtained from slurry rheology tests. Thecrucial parameters for pump selection are shear stress at certain shearrates, viscosity of the slurry, yield point, and settlement rate of theslurry. Other physical properties such as attrition and the friction ofparticles inside the slurry may also need to be considered for pumpselection. The shear rate and shear stress curve of coal-water andwood-water slurry coordinates can be characterized by the GeneralizedBingham Plastic model [10] as shown in Eq. 1. where τ is shear stressapplied to the system when the shear rate of γ is maintained. τy is theyield stress of the starting slurry. K and n are empirical parametersdetermined by fitting the equation with experimental data. Thecorrelation between shear rate and shear stress corresponds to a powerlaw with constant coefficient of K. Thus, the viscosity of the slurry isdefined as the slope of change in shear rate with a change in shearstress as given by Eq. 2. A change in viscosity can be obtained byeither shear thinning or shear thickening. In shear thinning flow theviscosity decreases with increasing shear rate, while in shearthickening flow, viscosity increases with increasing shear rate.

$\begin{matrix}{\tau = {\tau_{y} + {K\;\gamma^{n}}}} & \left( {{Eq}.\mspace{14mu} 1} \right) \\{\mu = \frac{\Delta\;\tau}{\Delta\;\gamma}} & \left( {{Eq}.\mspace{14mu} 2} \right)\end{matrix}$

Results and Discussion of Experiment 5

A. Effect of Shear Rate on Viscosity

The effect of an increase in shear rate on slurry viscosity wasevaluated for different particle sizes and solid loading for bothcoal-water and wood-water slurries. The relationship between shear rateand viscosity was obtained for different particle sizes for coal-waterand wood-water slurries. The results are shown in FIG. 3 and FIG. 4,respectively. The solid loading in the coal-water and wood slurries wasfixed at 60 wt. % and 10 wt. %, respectively.

Non-Newtonian shear thinning was observed for both coal-water andwood-water slurries. The viscosity of the coal-water slurries, shown inFIG. 3, decreased rapidly with increased shear rate up to 200 s⁻¹ butthen reduced at a slower rate beyond 200 s⁻¹. Also, larger particlesizes had lower slurry viscosity. A similar trend was observed inwood-water slurries tests as seen in FIG. 4. The viscosity of wood-waterslurries decreased rapidly with increased shear rates of up to 100 s⁻¹but decreased at a slower rate beyond 100 s⁻¹. Similar to the coal-waterslurries, the viscosity decreased with increasing particle size. Acomparison of these two figures show that much higher shear thinningproperties was observed for wood-water slurries. A possible reason maybe that water is highly hydrogen bonded with wood particles. Therefore,higher shear stress was needed for wood-water slurries to maintain asame shear rate compared to coal-water slurries.

B. Effect of Solid Content

The maximum solid loading in coal-water and wood-water slurries variedfor different particle size. When the maximum solid loading wasexceeded, the mixture was not uniform as slurry and particles boundtogether to form larger particles. Table 2 shows the maximum solidloading for coal-water and wood-water slurries.

TABLE 2 Maximum solid loading in wood-water and coal-water slurriesMaximum wood loading Maximum coal loading in slurry (wt. %) in slurry(wt. %) 0-150 μm 13% 65% 150 μm-250 μm 13.5%   66.5%   250 μm-500 μm 15%68%

Experimental results for different solid loading on coal-water and woodwater slurries are shown in FIG. 5 and FIG. 6, respectively.

It can be seen from FIG. 5 that the coal-water slurries changed from ashear thinning property to a shear thickening property as thecoal-loading decreased from 50 wt. % to 45 wt %. The shear thickeningproperty of coal-water slurry was rarely observed by other studies. S.K. Majumder reported [11] that the reason for the thickening was due tothe emulsion-solids exhibiting dilatants flow behavior with low solidloading range. It is also seen that the viscosity of coal-water slurriesincreased with increasing solid loading. There was not much differencebetween slurries with solid loading of less than 55 wt. % for shearrates over 150 s⁻¹. Similar to the coal-water slurries, the viscosity ofwood-water slurries also increased with increasing solid loading.However, at a shear rate over 100 s⁻¹, Newtonian fluid properties wereobserved at solid loading less than 7.5 wt. % and the viscosityincreased slightly with increasing shear rate, as shown in FIG. 6.

C. Properties of Pretreated Wood-Water and Commingled Wood-Coal-WaterSlurries

The effect of shear rate on viscosity in pretreated wood-water slurrywas also evaluated. FIG. 7 shows the rheological properties ofpretreated biomass slurries with weight percentages of 20%, 30% and 40%.Unlike the wood-water slurry before pretreatment, the viscosity profileof pretreated wood-water slurry dropped rapidly as shear rate increasedfrom 10 s⁻¹ to 200 s⁻¹, then decreased slightly beyond 200 s⁻¹. Theviscosity increased with increasing solid loading which is consistentwith wood-water slurry before pretreatment. The important result is thatwith pretreatment there is an increase in the solid loading ofwood-water slurry to 40% as compared to 12.5% before pretreatment. It isbelieved that presence of hydrogen under up to 230° C. and 100 Psi helpbreak down the cellulose and semi-cellulose structure of wood whichresulted in breaking the hydrogen bond between the wood and water.However, no analytical experiments were performed to confirm this.

FIG. 8 shows the comparison of the viscosity of slurries with increasingsolid loading. It is clear that the pretreatment process greatly helpedincrease the solid content in wood-water slurry at a similar viscosity.At the same viscosity, the coal-water slurry had the highest solidcontent. The commingled coal in pretreated wood-water slurry had a solidcontent up to 55 wt. %.

D. Solid Loading of Pumpable Slurries

We have found that a viscosity of less than 0.7 Pas is preferred foreasy pumping of slurries to our reactor. We successfully increased thesolid loading in the wood-water slurry by using our pretreatment methodwhile maintaining the viscosity. The solid loading of pretreatedwood-water slurry under 0.7 Pas was less than 35%. We commingled thepretreated wood-water slurry with coal to increase its solid loading andcarbon content. The results of viscosity with increased solid loading ofcoal-water, wood-water, pretreated wood-water and commingled coal-woodwater slurries are shown in FIG. 8. It is shown that at 0.7 Pasviscosity, coal-water slurry had the highest solid loading of up to 65%,and wood-water slurry before pretreatment had the lowest solid loadingof less than 12.5%. After pretreatment, the solid loading in wood-waterslurry of 0.7 Pas increased to nearly 35% and when commingled with coal,the solid loading increased to nearly 45%. Closer investigation of thewater to carbon ratio of these slurries further suggested that thecommingled coal-wood water slurry provided a water to carbon ratio of2:1. With our gasification process the optimized water to carbon ratiois 3:1. Thus, with pretreatment, the rheological properties of thecommingled coal-wood water slurry are improved for use as a feedstockfor gasification. Such commingled coal-wood water slurries can beadjusted with water to obtain the desired water:carbon ratio of 3:1.

Table 3 shows the results of mass based water to carbon ratio ofdifferent slurries at a viscosity of 0.7 Pas.

TABLE 3 Mass based water to carbon ratio of slurries (0.7 Pas viscosity)wood- pretreated coal-water water wood-water commingled biomass- slurryslurry slurry coal-water slurry Ratio 0.78 13.82 3.67 2.01

The viscosity plot of different water carbon ratio in commingledcoal-wood water slurry is shown in FIG. 9. Under optimized water tocarbon ratio of 3:1 for application as feedstock in gasificationprocess, slurry viscosity is less than 0.45 Pas and provides goodpumpability.

In conclusion, our results show non-Newtonian properties of slurries andshear thinning behavior for most cases except the coal-water slurrieswith a solid content below 45%. Comparison of the viscosity of slurriesunder shear rate of 100 s⁻¹ shows that thermal pretreatment increasedthe solid loading of wood-water and commingled coal-biomass-waterslurries for the same viscosity values. Pretreatment of the commingledcoal-wood slurries provided a pumpable slurry with a solid carboncontent for optimum feed to the steam hydrogasification reactor.

Although the present invention and its advantages have been described indetail, it should be understood that various changes, substitutions andalterations can be made herein without departing from the spirit andscope of the invention as defined by the appended claims. Moreover, thescope of the present application is not intended to be limited to theparticular embodiments of the process and apparatus described in thespecification. As one of ordinary skill in the art will readily,appreciate from the disclosure of the present invention, processes andapparatuses, presently existing or later to be developed that performsubstantially the same function or achieve substantially the same resultas the corresponding embodiments described herein may be utilizedaccording to the present invention. Accordingly, the appended claims areintended to include such processes and use of such apparatuses withintheir scope.

REFERENCES ALL OF WHICH ARE INCLUDED BY REFERENCE IN THEIR ENTIRETY

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The invention claimed is:
 1. A process for producing a pumpable highcarbon content slurry comprising: providing a mixture of water and amaterial selected from the group consisting of an agricultural product,wood, plant, paper and cardboard, wherein the material comprises aweight percentage between 30 wt % to 70 wt % of the mixture; mixing themixture with a residue produced from a waste water treatment process toform a slurry mixture; and heating the slurry mixture under anon-oxidative gas to thereby produce the high carbon content slurry. 2.The process of claim 1, wherein the non-oxidative gas is selected fromthe group consisting of argon, helium, nitrogen, hydrogen, carbondioxide, or gaseous hydrocarbons, or mixtures thereof.
 3. The process ofclaim 1 in which the slurry mixture is heated to the temperature havinga range of 170 to 250° C.
 4. The process of claim 1, wherein the slurrymixture is heated under the non-oxidative gas at a pressure of 100 to400 psi.
 5. A process for converting biomass into a higher carboncontent slurry, consisting essentially of: grinding the biomass; mixingthe biomass with water to thereby form a first mixture, wherein thebiomass comprises a weight percentage between 30 wt % to 70 wt % of thefirst mixture; mixing the first mixture with a residue produced from awaste water treatment process to form a slurry mixture; and heating theslurry mixture under a non-oxidative gas to thereby produce the highcarbon content slurry.
 6. The process of claim 5, wherein the biomass isselected from the group consisting of an agricultural product, wood,plant, paper and cardboard.
 7. The process of claim 5, wherein thenon-oxidative gas is selected from the group consisting of argon,helium, nitrogen, hydrogen, carbon dioxide, or gaseous hydrocarbons, ormixtures thereof.
 8. The process of claim 5, the slurry mixture isheated under the non-oxidative gas at a pressure of 100 to 400 psi.